U.S. patent application number 16/005637 was filed with the patent office on 2019-03-28 for anti-uv plastic for automobile interior ornaments.
The applicant listed for this patent is Bin Chen, Ling Yin, Naitian Zhang, Rongfu Zhang. Invention is credited to Bin Chen, Ling Yin, Naitian Zhang, Rongfu Zhang.
Application Number | 20190092939 16/005637 |
Document ID | / |
Family ID | 61958133 |
Filed Date | 2019-03-28 |
United States Patent
Application |
20190092939 |
Kind Code |
A1 |
Zhang; Naitian ; et
al. |
March 28, 2019 |
Anti-UV plastic for automobile interior ornaments
Abstract
This invention discloses an anti-UV plastic for automobile
interior ornaments. The anti-UV plastic for automobile interior
ornaments includes PC resin, ABS resin, antioxygen, pentaerythritol
stearate, inorganic filler, anti-UV fiber, organic silicon resin or
modified organic silicon resin. Except maintaining the properties
of ABS resin and PC resin, the anti-UV plastic for automobile
interior ornaments has excellent mechanical properties and thermal
properties, and can reduce the maintenance cost of automobile
interior ornaments caused by UV aging. In addition, the anti-UV
plastic for automobile interior ornaments owns favorable machining
properties, and can be machined into automobile interior ornaments
of various shapes.
Inventors: |
Zhang; Naitian; (Hangzhou,
CN) ; Chen; Bin; (Hangzhou, CN) ; Zhang;
Rongfu; (Hangzhou, CN) ; Yin; Ling; (Hangzhou,
CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Zhang; Naitian
Chen; Bin
Zhang; Rongfu
Yin; Ling |
Hangzhou
Hangzhou
Hangzhou
Hangzhou |
|
CN
CN
CN
CN |
|
|
Family ID: |
61958133 |
Appl. No.: |
16/005637 |
Filed: |
June 11, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2205/03 20130101;
C08J 2483/04 20130101; C08J 3/203 20130101; C08J 2479/06 20130101;
C08L 69/00 20130101; C08L 2205/035 20130101; C08L 2205/16 20130101;
C08J 2469/00 20130101; C08L 55/02 20130101; C08J 2355/02 20130101;
C08L 55/02 20130101; C08L 2201/08 20130101 |
International
Class: |
C08L 55/02 20060101
C08L055/02; C08J 3/20 20060101 C08J003/20 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 8, 2017 |
CN |
201711295714X |
Claims
1. The anti-UV plastic for automobile interior ornaments is
characterized by that, it is made from the following materials: PC
resin, ABS resin, antioxygen, pentaerythritol stearate, inorganic
filler, anti-UV fiber, organic silicon resin or modified organic
silicon resin.
2. The anti-UV plastic for automobile interior ornaments according
to claim 1 is characterized by that it is made from the materials
which are prepared according to the following parts by weight: PC
resin 25-30 parts, ABS resin 50-70 parts, antioxygen 1-2 parts,
pentaerythritol stearate 1-3 parts, inorganic filler 0-5 parts,
anti-UV fiber 15-20 parts, organic silicon resin or modified
organic silicon resin 0.5-2 parts.
3. The anti-UV plastic for automobile interior ornaments according
to claim 2, is characterized by that the antioxygen is one or
several kinds among antioxygen 1098, antioxygen 1010, antioxygen
168, antioxygen 264, antioxygen T501 and antioxygen BHT.
4. The anti-UV plastic for automobile interior ornaments according
to claim 2, is characterized by that the modified organic silicon
resin is glass modified organic silicon resin. The anti-UV fiber is
hydroxyl modified PBO fiber.
5. The anti-UV plastic for automobile interior ornaments according
to claim 2, is characterized by that the preparation process of
hydroxyl modified PBO fiber is as follows: (1) 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid are used as polymerization monomers, and
polyphosphoric acid is used as the solvent to polymerize for
64.about.90 h under 65.about.185.degree. C. to gain the
pre-polymerization solution; (2) The pre-polymerization solution
gained in Step (1) is spun to get the fiber. The fiber is washed
with water and dried under vacuum condition to gain the hydroxyl
modified PBO fiber.
6. The anti-UV plastic for automobile interior ornaments according
to claim 2, is characterized by that the anti-UV fiber is hydroxyl
modified PBO/inorganic UV absorbent fiber. The preparation process
of hydroxyl modified PBO/inorganic UV absorbent fiber is as
follows: (1) 4,6-diaminodiphenyl diphenol hydrochloride,
2,5-dihydroxy terephthalic acid and terephthalic acid are used as
polymerization monomers, and polyphosphoric acid is used as the
solvent to polymerize for 34.about.44 h under 65.about.100.degree.
C. Then, the inorganic UV absorbent whose weight is 0.01-0.04 times
of weight of 4,6-diaminodiphenyl diphenol hydrochloride is added to
polymerize for 30.about.46 h under 130.about.185.degree. C. to gain
the pre-polymerization solution; (2) The pre-polymerization
solution gained in Step (1) is spun to get the fiber. The fiber is
washed with water and dried under vacuum condition to gain the
hydroxyl modified PBO/inorganic UV absorbent fiber.
7. The anti-UV plastic for automobile interior ornaments according
to claim 6, is characterized by that the inorganic UV absorbent is
one or the combination of titanium dioxide, zinc oxide and Zr doped
zinc oxide.
8. The anti-UV plastic for automobile interior ornaments according
to claim 2, is characterized by that the inorganic filler is one or
several kinds among talcum powder, mica powder, kaolin,
pyrophyllite powder, calcium carbonate, wollastonite, calcium
sulfate and carbon black.
9. The method to prepare the anti-UV plastic for automobile
interior ornaments is characterized by that, it includes the
following steps: S1 PC resin and ABS resin are dried respectively
for 3.about.5 h under 80.about.85.degree. C.; S2 PC resin, ABS
resin, antioxygen, pentaerythritol stearate, inorganic filler,
anti-UV fiber, organic silicon resin or modified organic silicon
resin are weighed according to the formula, and mixed for 5-10 min
at the speed of 3000-5000 rpm to get the mixture; S3 The mixture is
put in the extruder to extrude out. The temperature of feeding
segment of the extruder is 180.about.190.degree. C. The temperature
of mixing segment is 230.about.240.degree. C. The temperature of
machine head is 200.about.210.degree. C. The revolving speed of
main machine is 80 100 rpm. Then, cooling and cutting into
particles are conducted to get the anti-UV plastic for automobile
interior ornaments.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] The present application claims priority from Chinese
application No. 201711295714X filed Dec. 8, 2017 which is hereby
incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] This invention relates to plastic technology field, in
particular to an anti-UV plastic for automobile interior
ornaments.
BACKGROUND TECHNOLOGY
[0003] Automobile interior ornaments generally refer to car trunk
clapboard, interior decorative plate, instrument panel, armrest,
carpet, other parts and materials. Automobile interior ornaments
represent automobile image and decide automobile reputation and
quality as well as people's intention for automobile selection. In
addition, automobile interior ornaments as auxiliary accessories
undertake the functions of radiation resistance, vibration
attenuation, thermal insulation, sound absorption and sound
shielding. Automobile interior ornaments play a very important role
for automobile comfort and durability.
[0004] Most automobile interior ornaments are made from plastic and
other high polymer materials. Due to long-term exposure to
sunshine, automobile interior ornaments are faced with the threat
of sunlight radiation and aging more or less. UV radiation
seriously affects the service life of high-molecular polymer. The
environmental pollution caused by waste materials is an issue that
current society cannot evade. Thus, it is very significant to
research the anti-UV plastic for automobile interior ornaments in
daily production and life.
[0005] The invention with the application number of 201510271996.4
discloses an alloy plastic for automobile interior ornaments. The
alloy plastic for automobile interior ornaments is composed of the
raw materials with the mass percentage as follows: PC resin 60-80%,
ASA resin 10-20%, flexibilizer 2-6%, antioxygen 0.3-0.9%, UV
absorbent 0.2-0.6%, pentaerythritol stearate 0.1-0.3%, antistatic
agent 5-15%, and chain extender 0.2-0.6%.
BRIEF SUMMARY OF THE INVENTION
[0006] The purpose of this invention is implemented through the
following technical proposal:
[0007] The technical problem to be solved in this invention is to
provide an anti-UV plastic for automobile interior ornaments.
[0008] The anti-UV plastic for automobile interior ornaments are
made from the following raw materials: PC resin, ABS resin,
antioxygen, pentaerythritol stearate, inorganic filler, anti-UV
fiber, organic silicon resin or modified organic silicon resin.
[0009] To be specific, the anti-UV plastic for automobile interior
ornaments is made from the materials which are prepared according
to the following parts by weight: PC resin 25-30 parts, ABS resin
50-70 parts, antioxygen 1-2 parts, pentaerythritol stearate 1-3
parts, inorganic filler 0-5 parts, anti-UV fiber 15-20 parts,
organic silicon resin or modified organic silicon resin 0.5-2
parts.
[0010] The antioxygen is one or several kinds among antioxygen
1098, antioxygen 1010, antioxygen 168, antioxygen 264, antioxygen
T501 and antioxygen BHT.
[0011] The preparation process of the organic silicon resin is as
follows:
[0012] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3-0.4 times of weight of methyl trichlorosilane are
added in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67-0.75 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6-0.7 times of weight of methyl trichlorosilane
and diphenyl dichlorosilane whose weight is 0.5-0.6 times of weight
of methyl trichlorosilane are added and evenly mixed to get the
mixed liquid of raw materials. The temperature of feeding process
system is kept at 0-2.degree. C.
[0013] (2) Water, acetone and xylene are mixed under the
environment temperature of 5-10.degree. C. to get the reaction
solvent whose volume is 2-2.5 times of mixed liquid volume of raw
materials. Wherein, the volume of water is 2.8-3 times of that of
absolute ethyl alcohol in Step (1). The volume ratio of acetone and
xylene is 1:(10-11);
[0014] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50-55.degree. C. at
the speed of 2-3.degree. C./min. The mixed liquid is stirred for
40-60 min at the speed of 170-230 rpm. Then, it is put still for
4-6 h under 20-30.degree. C. Then, aqueous phase is discarded, and
organic phase is reserved. The organic phase is washed with the
sodium bicarbonate solution with mass fraction of 1-2%. Then,
saturated sodium chloride is used to wash the organic phase to be
neutral. The volume ratio of organic phase, sodium bicarbonate
solution and saturated sodium chloride is 1:(0.5-0.7):(2-3) to get
the pre-polymerization solution of organic silicon resin;
[0015] (4) Xylene is removed under the conditions of
100-120.degree. C. and vacuum degree 0.06-0.08 MPa to gain
condensed silanol. The temperature of condensed silanol rises to
150-170.degree. C., and thermal reaction is lasted for 1.5-2 h to
gain the organic silicon resin.
[0016] The preparation process of glass modified organic silicon
resin is as follows:
[0017] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3-0.4 times of weight of methyl trichlorosilane are
added in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67-0.75 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6-0.7 times of weight of methyl trichlorosilane
and diphenyl dichlorosilane whose weight is 0.5-0.6 times of weight
of methyl trichlorosilane are added and evenly mixed to get the
mixed liquid of raw materials. The temperature of feeding process
system is kept at 0-2.degree. C.
[0018] (2) Water, acetone and xylene are mixed under the
environment temperature of 5-10.degree. C. to get the reaction
solvent whose volume is 2-2.5 times of mixed liquid volume of raw
materials. Wherein, the volume of water is 2.8-3 times of that of
absolute ethyl alcohol in Step (1). The volume ratio of acetone and
xylene is 1:(10-11);
[0019] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50-55.degree. C. at
the speed of 2-3.degree. C./min. The mixed liquid is stirred for
40-60 min at the speed of 170-230 rpm. Then, it is put still for
4-6 h under 20-30.degree. C. Then, aqueous phase is discarded, and
organic phase is reserved. The organic phase is washed with the
sodium bicarbonate solution with mass fraction of 1-2%. Then,
saturated sodium chloride is used to wash the organic phase to be
neutral. The volume ratio of organic phase, sodium bicarbonate
solution and saturated sodium chloride is 1:(0.5-0.7):(2-3) to get
the pre-polymerization solution of organic silicon resin;
[0020] (4) The glass whose weight is 0.13-0.15 times of weight of
methyl trichlorosilane is added in the organic resin prepolymer and
mixed for 20-30 min at the speed of 170-230 rmp;
[0021] (5) Xylene is removed under the conditions of
100-120.degree. C. and vacuum degree 0.06-0.08 MPa to gain
condensed silanol. The temperature of condensed silanol rises to
150-170.degree. C., and thermal reaction is lasted for 1.5-2 h to
gain the glass modified organic silicon resin.
[0022] In some implementation ways of this invention, the anti-UV
fiber is hydroxyl modified PBO fiber. The preparation process of
hydroxyl modified PBO fiber is as follows:
[0023] (1) 4,6-diaminodiphenyl diphenol hydrochloride,
2,5-dihydroxy terephthalic acid and terephthalic acid are used as
polymerization monomers, and polyphosphoric acid is used as the
solvent to polymerize for 64.about.90 h under 65.about.185.degree.
C. to gain the pre-polymerization solution;
[0024] (2) The pre-polymerization solution gained in Step (1) is
spun to get the fiber. The fiber is washed with water and dried
under vacuum condition to gain the hydroxyl modified PBO fiber.
[0025] After hydroxyl group is introduced, the interface
adhesiveness between PBO fiber and resin matrix is enhanced. This
may be because the introduction of hydroxyl group significantly
improves surface activity of fiber, changes conjugate electron
cloud system in PBO and causes fiber surface activation, thus
enhancing interface adhesiveness property between fiber and matrix
material.
[0026] Optimally, the preparation process of hydroxyl modified PBO
fiber is as follows:
[0027] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid, terephthalic acid and polyphosphoric acid are
added in the reaction still. The molar ratio of 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid is 1:(0.05-0.5):(0.5-0.95). The addition amount
of polyphosphoric acid is 5-7 times of total weight of
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65-70.degree. C. at the speed of 2-3.degree. C./min. After stirring
for 18-24 h at the speed of 170-230 rpm, hydrogen chloride gas
escapes. The temperature rises to 80-100.degree. C. at the speed of
2-3.degree. C./min, and the solution is mixed for 16-20 h at the
speed of 170-230 rpm. In this period, vacuum is pumped under the
condition of vacuum degree 0.06-0.07 MPa. The generated hydrogen
chloride gas is pumped out. Then, the temperature continues to rise
to 130-135.degree. C. at the speed of 2-3.degree. C./min, and the
solution is stirred for 15-20 h at the speed of 170-230 rpm. The
viscosity increases. Next, the temperature continues to rise to
150-155.degree. C. at the speed of 2-3.degree. C./min, and the
solution is stirred for 10-16 h at the speed of 170-230 rpm. The
viscosity further increases. The temperature rises to
180-185.degree. C. at the speed of 2-3.degree. C./min, and the
solution is stirred for 5-10 h at the speed of 170-230 rpm to get
the prepolymerization solution.
[0028] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the screw extruder. The
temperature in the screw is set to 170-175.degree. C.,
175-180.degree. C. and 180-185.degree. C. respectively. The
prepolymerization solution is extruded out under the extrusion
pressure of 900-1000N. Then, jet stretch and solidification molding
are conducted. The spinneret plate has 16-18 holes. The diameter of
spinneret plate is 0.2-0.3 mm. The distance between spinneret
orifice and coagulating bath is 10-50 cm. The coagulating bath is
polyphosphoric acid solution with the mass fraction of 10-12%. The
temperature of coagulating bath is 20-30.degree. C. The winding
speed is 40-70 m/min. Finally, the fiber is gained. The fiber is
washed with the water whose weight is 50-100 times of fiber weight,
and is dried for 10-12 h under the conditions of 45-50.degree. C.
and vacuum degree 0.06-0.08 MPa to gain hydroxyl modified PBO
fiber.
[0029] In some implementation ways of this invention, the anti-UV
fiber is hydroxyl modified PBO/inorganic UV absorbent fiber. The
preparation process of hydroxyl modified PBO/inorganic UV absorbent
fiber is as follows:
[0030] (1) 4,6-diaminodiphenyl diphenol hydrochloride,
2,5-dihydroxy terephthalic acid and terephthalic acid are used as
polymerization monomers, and polyphosphoric acid is used as the
solvent to polymerize for 34.about.44 h under 65.about.100.degree.
C. The inorganic UV absorbent whose weight is 0.01-0.04 times of
weight of 4,6-diaminodiphenyl diphenol hydrochloride is added to
polymerize for 30.about.46 h under 130.about.185.degree. C. to get
the prepolymerization solution;
[0031] (2) The pre-polymerization solution gained in Step (1) is
spun to get the fiber. The fiber is washed with water and dried
under vacuum condition to gain the hydroxyl modified PBO/inorganic
UV absorbent fiber.
[0032] After hydroxyl group is introduced in PBO fiber, the
addition of inorganic UV absorbent can effectively inhibit the
occurrence and proceeding of PBO photooxidation degradation
reaction, delay molecular chain fracture, thus reduce decline rate
of fiber molecular weight and make it keep good mechanical
property.
[0033] Optimally, the preparation process of hydroxyl modified
PBO/inorganic UV absorbent fiber is as follows:
[0034] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid, terephthalic acid and polyphosphoric acid are
added in the reaction still. The molar ratio of 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid is 1:(0.05-0.5):(0.5-0.95). The addition amount
of polyphosphoric acid is 5-7 times of total weight of
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65-70.degree. C. at the speed of 2-3.degree. C./min. After stirring
for 18-24 h at the speed of 170-230 rpm, hydrogen chloride gas
escapes. The temperature rises to 80-100.degree. C. at the speed of
2-3.degree. C./min, and the solution is mixed for 16-20 h at the
speed of 170-230 rpm. In this period, vacuum is pumped under the
condition of vacuum degree 0.06-0.07 MPa. The generated hydrogen
chloride gas is pumped out. The inorganic UV absorbent whose weight
is 0.01-0.04 times of weight of 4,6-diaminodiphenyl diphenol
hydrochloride is added and mixed evenly. Then, the temperature
continues to rise to 130-135.degree. C. at the speed of 2-3.degree.
C./min, and the solution is stirred for 15-20 h at the speed of
170-230 rpm. The viscosity increases. Next, the temperature
continues to rise to 150-155.degree. C. at the speed of 2-3.degree.
C./min, and the solution is stirred for 10-16 h at the speed of
170-230 rpm. The viscosity further increases. The temperature rises
to 180-185.degree. C. at the speed of 2-3.degree. C./min, and the
solution is stirred for 5-10 h at the speed of 170-230 rpm to get
the prepolymerization solution.
[0035] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the screw extruder. The
temperature in the screw is set to 170-175.degree. C.,
175-180.degree. C. and 180-185.degree. C. respectively. The
prepolymerization solution is extruded out under the extrusion
pressure of 900-1000N. Then, jet stretch and solidification molding
are conducted. The spinneret plate has 16-18 holes. The diameter of
spinneret plate is 0.2-0.3 mm. The distance between spinneret
orifice and coagulating bath is 10-50 cm. The coagulating bath is
polyphosphoric acid solution with the mass fraction of 10-12%. The
temperature of coagulating bath is 20-30.degree. C. The winding
speed is 40-70 m/min. Finally, the fiber is gained. The fiber is
washed with the water whose weight is 50-100 times of fiber weight,
and is dried for 10-12 h under the conditions of 45-50.degree. C.
and vacuum degree 0.06-0.08 MPa to gain the hydroxyl modified
PBO/inorganic UV absorbent fiber.
[0036] The inorganic UV absorbent is one or the combination of
titanium dioxide, zinc oxide and Zr doped zinc oxide. Optimally,
the inorganic UV absorbent is the mixture of titanium dioxide and
Zr doped zinc oxide with the mass ratio of 1:(2-3).
[0037] The preparation process of Zr doped zinc oxide is as
follows: zinc nitrate water solution with the molar concentration
of 0.4-0.5 mol/L is prepared, and cetyl trimethyl ammonium bromide
is added. The solid-to-liquid ratio of cetyl trimethyl ammonium
bromide and zinc nitrate water solution is 0.008-0.009 g/mL, and
they are mixed evenly to get mixed liquid A. Sodium hydroxide water
liquid with the molar concentration of 1-2 mol/L is added under the
stirring condition of 170-230 rpm. The volume ratio of mixed liquid
A and sodium hydroxide water liquid is 1:(1-1.2), and they are
stirred for 20-30 min at the speed of 170-230 rpm to get the
material I. Zirconium dichloride hydrate and water are mixed at the
mass ratio of 1:(18-20). Then, sodium hydroxide whose weight is
1.7-1.9 times of weight of zirconium dichloride hydrate is added
and reacts for 30-40 min at the speed of 170-230 rpm to get the
reaction liquid. The reaction liquid is centrifuged for 15-25 min
at the speed of 2000-3000 rpm, and the solid at the bottom is
collected to get the material II. The material I and the material
II are mixed and heated to 140-150.degree. C. After thermal
insulation for 30-40 min, the mixture of material I and material II
is cooled to 20-25.degree. C., and the reaction product is
gathered. After the reaction product is washed respectively with
the water whose weight is 50-100 times of reaction product weight
and absolute ethyl alcohol whose weight is 40-70 times of reaction
product weight, it is dried for 8-12 h under the condition of
45-50.degree. C. and vacuum degree 0.06-0.08 MPa, and smashed to
particles with the grain size of 100-500 nm to gain the Zr doped
zinc oxide. Through doping transition metal ion, defects can be
introduced in the lattice in zinc oxide semiconductor, and the
crystallinity is changed. Meanwhile, the shielding effect of UV is
enhanced.
[0038] The inorganic filler is one or several kinds among talcum
powder, mica powder, kaolin, pyrophyllite powder, calcium
carbonate, wollastonite, calcium sulfate and carbon black.
[0039] The second technical problem to be solved by this invention
is to provide the method to prepare the anti-UV plastic for
automobile interior ornaments.
[0040] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0041] S1 PC resin and ABS resin are dried respectively for
3.about.5 h under 80.about.85.degree. C.;
[0042] S2 PC resin, ABS resin, antioxygen, pentaerythritol
stearate, inorganic filler, anti-UV fiber, organic silicon resin or
modified organic silicon resin are weighed according to the
formula, and mixed for 5-10 min at the speed of 3000-5000 rpm to
get the mixture;
[0043] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is
180.about.190.degree. C. The temperature of mixing segment is
230.about.240.degree. C. The temperature of machine head is
200.about.210.degree. C. The revolving speed of main machine is
80.about.100 rpm. Then, cooling and cutting into particles are
conducted to get the anti-UV plastic for automobile interior
ornaments.
[0044] Except maintaining the properties of ABS resin and PC resin,
the anti-UV plastic for automobile interior ornaments has excellent
mechanical properties and thermal properties, and can reduce the
maintenance cost of automobile interior ornaments caused by UV
aging. In addition, the anti-UV plastic for automobile interior
ornaments owns favorable machining properties, and can be machined
into automobile interior ornaments of various shapes.
DETAILED DESCRIPTION OF THE INVENTION
[0045] Introduction to various raw materials and instruments in the
implementation examples:
[0046] PC resin, purchased from Bayer, type number 1803
[0047] ABS resin, purchased from Taiwan Qimei, type number
PA-709s
[0048] Antioxygen 1010, CAS No.: 6683-19-8, purchased from BASF
China
[0049] Pentaerythritol stearate, CAS No.: 115-83-3, purchased from
TCI (Shanghai) Chemical Industry Co., Ltd.
[0050] Pyrophyllite powder, purchased from Lingshou Qianfu Mineral
Processing Plant, 500.
[0051] 4,6-diaminodiphenyl diphenol hydrochloride, CAS No.:
16523-31-2, purchased from TCI (Shanghai) Chemical Industry Co.,
Ltd.
[0052] Terephthalic acid, CAS No.: 100-21-0, purchased from
Shanghai Future Industrial Co., Ltd.
[0053] Polyphosphoric acid, purchased from Shanghai Meryer Chemical
Technology Co., Ltd.; the content of phosphorus pentoxide
84-85%
[0054] 2,5-dihydroxy terephthalic acid, CAS No.: 610-92-4,
purchased from Shangjai Chemsoon Technology Co., Ltd.
[0055] Methyl trichlorosilane, CAS No.: 75-79-6, purchased from
Shandong Xiaoye Chemical Co., Ltd.
[0056] Phenyl trichlorosilane, CAS No.: 98-13-5, purchased from
J&K Scientific Co., Ltd.
[0057] Dimethyldichlorosilance, CAS No.: 75-78-5, purchased from
Shanghai Worldyang Chemical Co., Limited
[0058] Diphenyl dichlorosilane, CAS No.: 80-10-4, purchased from
J&K Scientific Co., Ltd.
[0059] Titanium dioxide, rutile titanium dioxide from Shandong
Jiechen Chemical Co., Ltd. is smashed to the particles with grain
size of 100 nm
[0060] Zinc oxide, zinc oxide from Zhengzhou Runjia Chenical
Products Co., Ltd. is smashed to the particles with grain size of
100 nm
[0061] Glass, purchased from Lingshou Qianfu Mineral Processing
Plant, 500
[0062] Zirconium dichloride hydrate, CAS No.: 15461-27-5, purchased
from Meryer Chemical Technology Co., Ltd.
[0063] Cetyl trimethyl ammonium bromide, CAS No.: 57-09-0,
purchased from Shanghai Aladdin Biochemical Technology Co.,
Ltd.
Implementation Example 1
[0064] The anti-UV plastic for automobile interior ornaments is
made from the materials which are prepared according to the
following parts by weight: PC resin 30 parts, ABS resin 70 parts,
antioxygen 1010 2 parts, pentaerythritol stearate 3 parts,
pyrophyllite powder 5 parts, PBO fiber (length 0.6 mm) 20 parts,
organic silicon resin 2 parts.
[0065] The preparation process of PBO fiber is as follows:
[0066] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, terephthalic acid and
polyphosphoric acid are added in the reaction still. The molar
ratio of 4,6-diaminodiphenyl diphenol hydrochloride and
terephthalic acid is 1:1. The addition amount of polyphosphoric
acid is 5 times of total weight of 4,6-diaminodiphenyl diphenol
hydrochloride and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65.degree. C. at the speed of 2.degree. C./min. After stirring for
24 h at the speed of 170 rpm, hydrogen chloride gas escapes. The
temperature rises to 80.degree. C. at the speed of 2.degree.
C./min, and the solution is mixed for 20 h at the speed of 170 rpm.
In this period, vacuum is pumped under the condition of vacuum
degree 0.06 MPa. The generated hydrogen chloride gas is pumped out.
Then, the temperature continues to rise to 130.degree. C. at the
speed of 2.degree. C./min, and the solution is stirred for 20 h at
the speed of 170 rpm. The viscosity increases. Next, the
temperature continues to rise to 150.degree. C. at the speed of
2.degree. C./min, and the solution is stirred for 16 h at the speed
of 170 rpm. The viscosity further increases. The temperature rises
to 180.degree. C. at the speed of 2.degree. C./min, and the
solution is stirred for 10 h at the speed of 170 rpm to get the
prepolymerization solution.
[0067] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the single screw extruder.
The temperature in the screw is set to 170.degree. C., 175.degree.
C. and 180.degree. C. respectively. The prepolymerization solution
is extruded out under the extrusion pressure of 900N. Then, jet
stretch and solidification molding are conducted. The spinneret
plate has 18 holes. The diameter of spinneret plate is 0.3 mm. The
distance between spinneret orifice and coagulating bath is 35 cm.
The coagulating bath is polyphosphoric acid solution with the mass
fraction of 10%. The temperature of coagulating bath is 25.degree.
C. The winding speed is 50 m/min. Finally, the fiber is gained. The
fiber is washed with the water whose weight is 80 times of fiber
weight, and is dried for 12 h under the conditions of 45.degree. C.
and vacuum degree 0.07 MPa to gain the PBO fiber. The PBO fiber is
cut to the length of 0.6 mm.
[0068] The preparation process of the organic silicon resin is
[0069] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3 times of weight of methyl trichlorosilane are added
in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6 times of weight of methyl trichlorosilane and
diphenyl dichlorosilane whose weight is 0.5 times of weight of
methyl trichlorosilane are added and evenly mixed to get the mixed
liquid of raw materials. The temperature of feeding process system
is kept at 0.degree. C.
[0070] (2) Water, acetone and xylene are mixed under the
environment temperature of 5.degree. C. to get the reaction solvent
whose volume is 2 times of mixed liquid volume of raw materials.
Wherein, the volume of water is 2.8 times of that of absolute ethyl
alcohol in Step (1). The volume ratio of acetone and xylene is
1:10;
[0071] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50.degree. C. at the
speed of 2.degree. C./min. The mixed liquid is stirred for 40 min
at the speed of 170 rpm. Then, it is put still for 4 h under
20.degree. C. Then, aqueous phase is discarded, and organic phase
is reserved. The organic phase is washed with the sodium
bicarbonate solution with mass fraction of 1%. Then, saturated
sodium chloride is used to wash the organic phase to be neutral.
The volume ratio of organic phase, sodium bicarbonate solution and
saturated sodium chloride is 1:0.5:2 to get the pre-polymerization
solution of organic silicon resin;
[0072] (4) Xylene is removed under the conditions of 100.degree. C.
and vacuum degree 0.06 MPa to gain condensed silanol. The
temperature of condensed silanol rises to 150.degree. C., and
thermal reaction is lasted for 1.5 h to gain the glass modified
organic silicon resin.
[0073] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0074] S1 PC resin and ABS resin are dried respectively for 4 h
under 85.degree. C.;
[0075] S2 PC resin, ABS resin, antioxygen 1010, pentaerythritol
stearate, pyrophyllite powder, PBO fiber and organic silicon resin
are weighed according to the formula, and mixed for 8 min at the
speed of 3000 rpm to get the mixture;
[0076] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is 190.degree. C.
The temperature of mixing segment is 240.degree. C. The temperature
of machine head is 210.degree. C. The revolving speed of main
machine is 80 rpm. Then, cooling and cutting into cylindrical
particles with the diameter of 3 mm and length of 2 mm are
conducted to get the anti-UV plastic for automobile interior
ornaments.
Implementation Example 2
[0077] The anti-UV plastic for automobile interior ornaments is
made from the materials which are prepared according to the
following parts by weight: PC resin 30 parts, ABS resin 70 parts,
antioxygen 1010 2 parts, pentaerythritol stearate 3 parts,
pyrophyllite powder 5 parts, PBO fiber (length 0.6 mm) 20 parts,
glass modified organic silicon resin 2 parts.
[0078] The preparation process of PBO fiber is as follows:
[0079] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, terephthalic acid and
polyphosphoric acid are added in the reaction still. The molar
ratio of 4,6-diaminodiphenyl diphenol hydrochloride and
terephthalic acid is 1:1. The addition amount of polyphosphoric
acid is 5 times of total weight of 4,6-diaminodiphenyl diphenol
hydrochloride and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65.degree. C. at the speed of 2.degree. C./min. After stirring for
24 h at the speed of 170 rpm, hydrogen chloride gas escapes. The
temperature rises to 80.degree. C. at the speed of 2.degree.
C./min, and the solution is mixed for 20 h at the speed of 170 rpm.
In this period, vacuum is pumped under the condition of vacuum
degree 0.06 MPa. The generated hydrogen chloride gas is pumped out.
Then, the temperature continues to rise to 130.degree. C. at the
speed of 2.degree. C./min, and the solution is stirred for 20 h at
the speed of 170 rpm. The viscosity increases. Next, the
temperature continues to rise to 150.degree. C. at the speed of
2.degree. C./min, and the solution is stirred for 16 h at the speed
of 170 rpm. The viscosity further increases. The temperature rises
to 180.degree. C. at the speed of 2.degree. C./min, and the
solution is stirred for 10 h at the speed of 170 rpm to get the
prepolymerization solution.
[0080] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the single screw extruder.
The temperature in the screw is set to 170.degree. C., 175.degree.
C. and 180.degree. C. respectively. The prepolymerization solution
is extruded out under the extrusion pressure of 900N. Then, jet
stretch and solidification molding are conducted. The spinneret
plate has 18 holes. The diameter of spinneret plate is 0.3 mm. The
distance between spinneret orifice and coagulating bath is 35 cm.
The coagulating bath is polyphosphoric acid solution with the mass
fraction of 10%. The temperature of coagulating bath is 25.degree.
C. The winding speed is 50 m/min. Finally, the fiber is gained. The
fiber is washed with the water whose weight is 80 times of fiber
weight, and is dried for 12 h under the conditions of 45.degree. C.
and vacuum degree 0.07 MPa to gain the PBO fiber. The PBO fiber is
cut to the length of 0.6 mm.
[0081] The preparation process of glass modified organic silicon
resin is as follows:
[0082] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3 times of weight of methyl trichlorosilane are added
in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6 times of weight of methyl trichlorosilane and
diphenyl dichlorosilane whose weight is 0.5 times of weight of
methyl trichlorosilane are added and evenly mixed to get the mixed
liquid of raw materials. The temperature of feeding process system
is kept at 0.degree. C.
[0083] (2) Water, acetone and xylene are mixed under the
environment temperature of 5.degree. C. to get the reaction solvent
whose volume is 2 times of mixed liquid volume of raw materials.
Wherein, the volume of water is 2.8 times of that of absolute ethyl
alcohol in Step (1). The volume ratio of acetone and xylene is
1:10;
[0084] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50.degree. C. at the
speed of 2.degree. C./min. The mixed liquid is stirred for 40 min
at the speed of 170 rpm. Then, it is put still for 4 h under
20.degree. C. Then, aqueous phase is discarded, and organic phase
is reserved. The organic phase is washed with the sodium
bicarbonate solution with mass fraction of 1%. Then, saturated
sodium chloride is used to wash the organic phase to be neutral.
The volume ratio of organic phase, sodium bicarbonate solution and
saturated sodium chloride is 1:0.5:2 to get the pre-polymerization
solution of organic silicon resin;
[0085] (4) The glass whose weight is 0.13 times of weight of methyl
trichlorosilane is added in the organic resin prepolymer and mixed
for 20 min at the speed of 170 rmp;
[0086] (5) Xylene is removed under the conditions of 100.degree. C.
and vacuum degree 0.06 MPa to gain condensed silanol. The
temperature of condensed silanol rises to 150.degree. C., and
thermal reaction is lasted for 1.5 h to gain the glass modified
organic silicon resin.
[0087] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0088] S1 PC resin and ABS resin are dried respectively for 4 h
under 85.degree. C.;
[0089] S2 PC resin, ABS resin, antioxygen 1010, pentaerythritol
stearate, pyrophyllite powder, PBO fiber and glass modified organic
silicon resin are weighed according to the formula, and mixed for 8
min at the speed of 3000 rpm to get the mixture;
[0090] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is 190.degree. C.
The temperature of mixing segment is 240.degree. C. The temperature
of machine head is 210.degree. C. The revolving speed of main
machine is 80 rpm. Then, cooling and cutting into cylindrical
particles with the diameter of 3 mm and length of 2 mm are
conducted to get the anti-UV plastic for automobile interior
ornaments.
Implementation Example 3
[0091] The anti-UV plastic for automobile interior ornaments is
made from the materials which are prepared according to the
following parts by weight: PC resin 30 parts, ABS resin 70 parts,
antioxygen 1010 2 parts, pentaerythritol stearate 3 parts,
pyrophyllite powder 5 parts, PBO fiber (length 0.6 mm) 20 parts,
organic silicon resin 2 parts.
[0092] The preparation process of hydroxyl modified PBO fiber is as
follows:
[0093] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid, terephthalic acid and polyphosphoric acid are
added in the reaction still. The molar ratio of 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid is 1:0.35:0.65. The addition amount of
polyphosphoric acid is 5 times of total weight of
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65.degree. C. at the speed of 2.degree. C./min. After stirring for
24 h at the speed of 170 rpm, hydrogen chloride gas escapes. The
temperature rises to 80.degree. C. at the speed of 2.degree.
C./min, and the solution is mixed for 20 h at the speed of 170 rpm.
In this period, vacuum is pumped under the condition of vacuum
degree 0.06 MPa. The generated hydrogen chloride gas is pumped out.
Then, the temperature continues to rise to 130.degree. C. at the
speed of 2.degree. C./min, and the solution is stirred for 20 h at
the speed of 170 rpm. The viscosity increases. Next, the
temperature continues to rise to 150.degree. C. at the speed of
2.degree. C./min, and the solution is stirred for 16 h at the speed
of 170 rpm. The viscosity further increases. The temperature rises
to 180.degree. C. at the speed of 2.degree. C./min, and the
solution is stirred for 10 h at the speed of 170 rpm to get the
prepolymerization solution.
[0094] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the single screw extruder.
The temperature in the screw is set to 170.degree. C., 175.degree.
C. and 180.degree. C. respectively. The prepolymerization solution
is extruded out under the extrusion pressure of 900 N. Then, jet
stretch and solidification molding are conducted. The spinneret
plate has 18 holes. The diameter of spinneret plate is 0.3 mm. The
distance between spinneret orifice and coagulating bath is 35 cm.
The coagulating bath is polyphosphoric acid solution with the mass
fraction of 10%. The temperature of coagulating bath is 25.degree.
C. The winding speed is 50 m/min. Finally, the fiber is gained. The
fiber is washed with the water whose weight is 80 times of fiber
weight, and is dried for 12 h under the conditions of 45.degree. C.
and vacuum degree 0.07 MPa to gain the hydroxyl modified PBO fiber.
The hydroxyl modified PBO fiber is cut to the length of 0.6 mm.
[0095] The preparation process of glass modified organic silicon
resin is as follows:
[0096] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3 times of weight of methyl trichlorosilane are added
in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6 times of weight of methyl trichlorosilane and
diphenyl dichlorosilane whose weight is 0.5 times of weight of
methyl trichlorosilane are added and evenly mixed to get the mixed
liquid of raw materials. The temperature of feeding process system
is kept at 0.degree. C.
[0097] (2) Water, acetone and xylene are mixed under the
environment temperature of 5.degree. C. to get the reaction solvent
whose volume is 2 times of mixed liquid volume of raw materials.
Wherein, the volume of water is 2.8 times of that of absolute ethyl
alcohol in Step (1). The volume ratio of acetone and xylene is
1:10;
[0098] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50.degree. C. at the
speed of 2.degree. C./min. The mixed liquid is stirred for 40 min
at the speed of 170 rpm. Then, it is put still for 4 h under
20.degree. C. Then, aqueous phase is discarded, and organic phase
is reserved. The organic phase is washed with the sodium
bicarbonate solution with mass fraction of 1%. Then, saturated
sodium chloride is used to wash the organic phase to be neutral.
The volume ratio of organic phase, sodium bicarbonate solution and
saturated sodium chloride is 1:0.5:2 to get the pre-polymerization
solution of organic silicon resin;
[0099] (4) The glass whose weight is 0.13 times of weight of methyl
trichlorosilane is added in the organic resin prepolymer and mixed
for 20 min at the speed of 170 rmp;
[0100] (5) Xylene is removed under the conditions of 100.degree. C.
and vacuum degree 0.06 MPa to gain condensed silanol. The
temperature of condensed silanol rises to 150.degree. C., and
thermal reaction is lasted for 1.5 h to gain the glass modified
organic silicon resin.
[0101] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0102] S1 PC resin and ABS resin are dried respectively for 4 h
under 85.degree. C.;
[0103] S2 PC resin, ABS resin, antioxygen 1010, pentaerythritol
stearate, pyrophyllite powder, hydroxyl modified PBO fiber and
glass modified organic silicon resin are weighed according to the
formula, and mixed for 8 min at the speed of 3000 rpm to get the
mixture;
[0104] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is 190.degree. C.
The temperature of mixing segment is 240.degree. C. The temperature
of machine head is 210.degree. C. The revolving speed of main
machine is 80 rpm. Then, cooling and cutting into cylindrical
particles with the diameter of 3 mm and length of 2 mm are
conducted to get the anti-UV plastic for automobile interior
ornaments.
Implementation Example 4
[0105] The anti-UV plastic for automobile interior ornaments is
made from the materials which are prepared according to the
following parts by weight: PC resin 30 parts, ABS resin 70 parts,
antioxygen 1010 2 parts, pentaerythritol stearate 3 parts,
pyrophyllite powder 5 parts, hydroxyl modified PBO/titanium dioxide
fiber (length 0.6 mm) 20 parts, glass modified organic silicon
resin 2 parts.
[0106] The preparation process of hydroxyl modified PBO/titanium
dioxide fiber is as follows:
[0107] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid, terephthalic acid and polyphosphoric acid are
added in the reaction still. The molar ratio of 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid is 1:0.35:0.65. The addition amount of
polyphosphoric acid is 5 times of total weight of
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65.degree. C. at the speed of 2.degree. C./min. After stirring for
24 h at the speed of 170 rpm, hydrogen chloride gas escapes. The
temperature rises to 80.degree. C. at the speed of 2.degree.
C./min, and the solution is mixed for 20 h at the speed of 170 rpm.
In this period, vacuum is pumped under the condition of vacuum
degree 0.06 MPa. The generated hydrogen chloride gas is pumped out.
Titanium dioxide whose weight is 0.04 times of 4,6-diaminodiphenyl
diphenol hydrochloride is added and mixed evenly. Then, the
temperature continues to rise to 130.degree. C. at the speed of
2.degree. C./min, and the solution is stirred for 20 h at the speed
of 170 rpm. The viscosity increases. Next, the temperature
continues to rise to 150.degree. C. at the speed of 2.degree.
C./min, and the solution is stirred for 16 h at the speed of 170
rpm. The viscosity further increases. The temperature rises to
180.degree. C. at the speed of 2.degree. C./min, and the solution
is stirred for 10 h at the speed of 170 rpm to get the
prepolymerization solution.
[0108] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the single screw extruder.
The temperature in the screw is set to 170.degree. C., 175.degree.
C. and 180.degree. C. respectively. The prepolymerization solution
is extruded out under the extrusion pressure of 900N. Then, jet
stretch and solidification molding are conducted. The spinneret
plate has 18 holes. The diameter of spinneret plate is 0.3 mm. The
distance between spinneret orifice and coagulating bath is 35 cm.
The coagulating bath is polyphosphoric acid solution with the mass
fraction of 10%. The temperature of coagulating bath is 25.degree.
C. The winding speed is 50 m/min. Finally, the fiber is gained. The
fiber is washed with the water whose weight is 80 times of fiber
weight, and is dried for 12 h under the conditions of 45.degree. C.
and vacuum degree 0.07 MPa to gain the hydroxyl modified
PBO/titanium dioxide fiber. The hydroxyl modified PBO/titanium
dioxide fiber is cut to the length of 0.6 mm.
[0109] The preparation process of glass modified organic silicon
resin is as follows:
[0110] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3 times of weight of methyl trichlorosilane are added
in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6 times of weight of methyl trichlorosilane and
diphenyl dichlorosilane whose weight is 0.5 times of weight of
methyl trichlorosilane are added and evenly mixed to get the mixed
liquid of raw materials. The temperature of feeding process system
is kept at 0.degree. C.
[0111] (2) Water, acetone and xylene are mixed under the
environment temperature of 5.degree. C. to get the reaction solvent
whose volume is 2 times of mixed liquid volume of raw materials.
Wherein, the volume of water is 2.8 times of that of absolute ethyl
alcohol in Step (1). The volume ratio of acetone and xylene is
1:10;
[0112] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50.degree. C. at the
speed of 2.degree. C./min. The mixed liquid is stirred for 40 min
at the speed of 170 rpm. Then, it is put still for 4 h under
20.degree. C. Then, aqueous phase is discarded, and organic phase
is reserved. The organic phase is washed with the sodium
bicarbonate solution with mass fraction of 1%. Then, saturated
sodium chloride is used to wash the organic phase to be neutral.
The volume ratio of organic phase, sodium bicarbonate solution and
saturated sodium chloride is 1:0.5:2 to get the pre-polymerization
solution of organic silicon resin;
[0113] (4) The glass whose weight is 0.13 times of weight of methyl
trichlorosilane is added in the organic resin prepolymer and mixed
for 20 min at the speed of 170 rmp;
[0114] (5) Xylene is removed under the conditions of 100.degree. C.
and vacuum degree 0.06 MPa to gain condensed silanol. The
temperature of condensed silanol rises to 150.degree. C., and
thermal reaction is lasted for 1.5 h to gain the glass modified
organic silicon resin.
[0115] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0116] S1 PC resin and ABS resin are dried respectively for 4 h
under 85.degree. C.;
[0117] S2 PC resin, ABS resin, antioxygen 1010, pentaerythritol
stearate, pyrophyllite powder, hydroxyl modified PBO/titanium
dioxide fiber and glass modified organic silicon resin are weighed
according to the formula, and mixed for 8 min at the speed of 3000
rpm to get the mixture;
[0118] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is 190.degree. C.
The temperature of mixing segment is 240.degree. C. The temperature
of machine head is 210.degree. C. The revolving speed of main
machine is 80 rpm. Then, cooling and cutting into cylindrical
particles with the diameter of 3 mm and length of 2 mm are
conducted to get the anti-UV plastic for automobile interior
ornaments.
[0119] Scratch resistance is tested for implementation example 4 by
referring to ASTM G 171-03. It is found that, obvious scratch can
be seen with naked eyes, and it is rough and not smooth. Besides,
peeling is very obvious.
Implementation Example 5
[0120] The anti-UV plastic for automobile interior ornaments is
made from the materials which are prepared according to the
following parts by weight: PC resin 30 parts, ABS resin 70 parts,
antioxygen 1010 2 parts, pentaerythritol stearate 3 parts,
pyrophyllite powder 5 parts, hydroxyl modified PBO/Zr doped zinc
oxide fiber (length 0.6 mm) 20 parts, glass modified organic
silicon resin 2 parts.
[0121] The preparation process of hydroxyl modified PBO/Zr doped
zinc oxide fiber is as follows:
[0122] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid, terephthalic acid and polyphosphoric acid are
added in the reaction still. The molar ratio of 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid is 1:0.35:0.65. The addition amount of
polyphosphoric acid is 5 times of total weight of
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65.degree. C. at the speed of 2.degree. C./min. After stirring for
24 h at the speed of 170 rpm, hydrogen chloride gas escapes. The
temperature rises to 80.degree. C. at the speed of 2.degree.
C./min, and the solution is mixed for 20 h at the speed of 170 rpm.
In this period, vacuum is pumped under the condition of vacuum
degree 0.06 MPa. The generated hydrogen chloride gas is pumped out.
Zr doped zinc oxide whose weight is 0.04 times of
4,6-diaminodiphenyl diphenol hydrochloride is added and mixed
evenly. Then, the temperature continues to rise to 130.degree. C.
at the speed of 2.degree. C./min, and the solution is stirred for
20 h at the speed of 170 rpm. The viscosity increases. Next, the
temperature continues to rise to 150.degree. C. at the speed of
2.degree. C./min, and the solution is stirred for 16 h at the speed
of 170 rpm. The viscosity further increases. The temperature rises
to 180.degree. C. at the speed of 2.degree. C./min, and the
solution is stirred for 10 h at the speed of 170 rpm to get the
prepolymerization solution.
[0123] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the single screw extruder.
The temperature in the screw is set to 170.degree. C., 175.degree.
C. and 180.degree. C. respectively. The prepolymerization solution
is extruded out under the extrusion pressure of 900N. Then, jet
stretch and solidification molding are conducted. The spinneret
plate has 18 holes. The diameter of spinneret plate is 0.3 mm. The
distance between spinneret orifice and coagulating bath is 35 cm.
The coagulating bath is polyphosphoric acid solution with the mass
fraction of 10%. The temperature of coagulating bath is 25.degree.
C. The winding speed is 50 m/min. Finally, the fiber is gained. The
fiber is washed with the water whose weight is 80 times of fiber
weight, and is dried for 12 h under the conditions of 45.degree. C.
and vacuum degree 0.07 MPa to gain the hydroxyl modified PBO/Zr
doped zinc oxide fiber. The hydroxyl modified PBO/Zr doped zinc
oxide fiber is cut to the length of 0.6 mm.
[0124] The preparation process of glass modified organic silicon
resin is as follows:
[0125] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3 times of weight of methyl trichlorosilane are added
in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6 times of weight of methyl trichlorosilane and
diphenyl dichlorosilane whose weight is 0.5 times of weight of
methyl trichlorosilane are added and evenly mixed to get the mixed
liquid of raw materials. The temperature of feeding process system
is kept at 0.degree. C.
[0126] (2) Water, acetone and xylene are mixed under the
environment temperature of 5.degree. C. to get the reaction solvent
whose volume is 2 times of mixed liquid volume of raw materials.
Wherein, the volume of water is 2.8 times of that of absolute ethyl
alcohol in Step (1). The volume ratio of acetone and xylene is
1:10;
[0127] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50.degree. C. at the
speed of 2.degree. C./min. The mixed liquid is stirred for 40 min
at the speed of 170 rpm. Then, it is put still for 4 h under
20.degree. C. Then, aqueous phase is discarded, and organic phase
is reserved. The organic phase is washed with the sodium
bicarbonate solution with mass fraction of 1%. Then, saturated
sodium chloride is used to wash the organic phase to be neutral.
The volume ratio of organic phase, sodium bicarbonate solution and
saturated sodium chloride is 1:0.5:2 to get the pre-polymerization
solution of organic silicon resin;
[0128] (4) The glass whose weight is 0.13 times of weight of methyl
trichlorosilane is added in the organic resin prepolymer and mixed
for 20 min at the speed of 170 rmp;
[0129] (5) Xylene is removed under the conditions of 100.degree. C.
and vacuum degree 0.06 MPa to gain condensed silanol. The
temperature of condensed silanol rises to 150.degree. C., and
thermal reaction is lasted for 1.5 h to gain the glass modified
organic silicon resin.
[0130] The preparation process of Zr doped zinc oxide is as
follows: zinc nitrate water solution with the molar concentration
of 0.5 mol/L is prepared, and cetyl trimethyl ammonium bromide is
added. The solid-to-liquid ratio of cetyl trimethyl ammonium
bromide and zinc nitrate water solution is 0.009 g/mL, and they are
mixed evenly to get mixed liquid A. Sodium hydroxide water liquid
with the molar concentration of 2 mol/L is added under the stirring
condition of 230 rpm. The volume ratio of mixed liquid A and sodium
hydroxide water liquid is 1:1.2, and they are stirred for 30 min at
the speed of 230 rpm to get the material I. Zirconium dichloride
hydrate and water are mixed at the mass ratio of 1:20. Then, sodium
hydroxide whose weight is 1.9 times of weight of zirconium
dichloride hydrate is added and reacts for 40 min at the speed of
230 rpm to get the reaction liquid. The reaction liquid is
centrifuged for 25 min at the speed of 3000 rpm, and the solid at
the bottom is collected to get the material II. The material I and
the material II are mixed and heated to 150.degree. C. After
thermal insulation for 40 min, the mixture of material I and
material II is cooled to 25.degree. C., and the reaction product is
gathered. After the reaction product is washed respectively with
the water whose weight is 100 times of reaction product weight and
absolute ethyl alcohol whose weight is 70 times of reaction product
weight, it is dried for 12 h under the condition of 50.degree. C.
and vacuum degree 0.08 MPa, and smashed to particles with the grain
size of 100 nm to gain the Zr doped zinc oxide.
[0131] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0132] S1 PC resin and ABS resin are dried respectively for 4 h
under 85.degree. C.;
[0133] S2 PC resin, ABS resin, antioxygen 1010, pentaerythritol
stearate, pyrophyllite powder, hydroxyl modified PBO/Zr doped zinc
oxide fiber and glass modified organic silicon resin are weighed
according to the formula, and mixed for 8 min at the speed of 3000
rpm to get the mixture;
[0134] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is 190.degree. C.
The temperature of mixing segment is 240.degree. C. The temperature
of machine head is 210.degree. C. The revolving speed of main
machine is 80 rpm. Then, cooling and cutting into cylindrical
particles with the diameter of 3 mm and length of 2 mm are
conducted to get the anti-UV plastic for automobile interior
ornaments.
[0135] Scratch resistance is tested for implementation example 5 by
referring to ASTM G 171-03. It is found that, no obvious scratch
can be seen with naked eyes, and the obvious scratch can be seen
when the magnifying lens is magnified for 300 times.
Implementation Example 6
[0136] The anti-UV plastic for automobile interior ornaments is
made from the materials which are prepared according to the
following parts by weight: PC resin 30 parts, ABS resin 70 parts,
antioxygen 1010 2 parts, pentaerythritol stearate 3 parts,
pyrophyllite powder 5 parts, hydroxyl modified PBO/titanium
dioxide/Zr doped zinc oxide fiber (length 0.6 mm) 20 parts, glass
modified organic silicon resin 2 parts.
[0137] The preparation process of hydroxyl modified PBO/titanium
dioxide/Zr doped zinc oxide fiber is as follows:
[0138] (1) Preparation of prepolymerization solution:
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid, terephthalic acid and polyphosphoric acid are
added in the reaction still. The molar ratio of 4,6-diaminodiphenyl
diphenol hydrochloride, 2,5-dihydroxy terephthalic acid and
terephthalic acid is 1:0.35:0.65. The addition amount of
polyphosphoric acid is 5 times of total weight of
4,6-diaminodiphenyl diphenol hydrochloride, 2,5-dihydroxy
terephthalic acid and terephthalic acid, and then they are mixed
evenly. Under nitrogen protection, the temperature rises to
65.degree. C. at the speed of 2.degree. C./min. After stirring for
24 h at the speed of 170 rpm, hydrogen chloride gas escapes. The
temperature rises to 80.degree. C. at the speed of 2.degree.
C./min, and the solution is mixed for 20 h at the speed of 170 rpm.
In this period, vacuum is pumped under the condition of vacuum
degree 0.06 MPa. The generated hydrogen chloride gas is pumped out.
Inorganic UV absorbent whose weight is 0.04 times of
4,6-diaminodiphenyl diphenol hydrochloride is added. The inorganic
UV absorbent is the mixture of titanium dioxide and Zr doped zinc
oxide with the mass ratio of 1:2. Then, the temperature continues
to rise to 130.degree. C. at the speed of 2.degree. C./min, and the
solution is stirred for 20 h at the speed of 170 rpm. The viscosity
increases. Next, the temperature continues to rise to 150.degree.
C. at the speed of 2.degree. C./min, and the solution is stirred
for 16 h at the speed of 170 rpm. The viscosity further increases.
The temperature rises to 180.degree. C. at the speed of 2.degree.
C./min, and the solution is stirred for 10 h at the speed of 170
rpm to get the prepolymerization solution.
[0139] (2) Fiber spinning and forming: the prepolymerization
solution gained in Step (1) is fed into the single screw extruder.
The temperature in the screw is set to 170.degree. C., 175.degree.
C. and 180.degree. C. respectively. The prepolymerization solution
is extruded out under the extrusion pressure of 900N. Then, jet
stretch and solidification molding are conducted. The spinneret
plate has 18 holes. The diameter of spinneret plate is 0.3 mm. The
distance between spinneret orifice and coagulating bath is 35 cm.
The coagulating bath is polyphosphoric acid solution with the mass
fraction of 10%. The temperature of coagulating bath is 25.degree.
C. The winding speed is 50 m/min. Finally, the fiber is gained. The
fiber is washed with the water whose weight is 80 times of fiber
weight, and is dried for 12 h under the conditions of 45.degree. C.
and vacuum degree 0.07 MPa to gain the hydroxyl modified
PBO/titanium dioxide/Zr doped zinc oxide fiber. The hydroxyl
modified PBO/titanium dioxide/Zr doped zinc oxide fiber is cut to
the length of 0.6 mm.
[0140] The preparation process of glass modified organic silicon
resin is as follows:
[0141] (1) Methyl trichlorosilane and phenyl trichlorosilane whose
weight is 0.3 times of weight of methyl trichlorosilane are added
in the reaction vessel and mixed evenly. Then, absolute ethyl
alcohol whose weight is 0.67 times of weight of methyl
trichlorosilane is added and evenly mixed. Dimethyldichlorosilance
whose weight is 0.6 times of weight of methyl trichlorosilane and
diphenyl dichlorosilane whose weight is 0.5 times of weight of
methyl trichlorosilane are added and evenly mixed to get the mixed
liquid of raw materials. The temperature of feeding process system
is kept at 0.degree. C.
[0142] (2) Water, acetone and xylene are mixed under the
environment temperature of 5.degree. C. to get the reaction solvent
whose volume is 2 times of mixed liquid volume of raw materials.
Wherein, the volume of water is 2.8 times of that of absolute ethyl
alcohol in Step (1). The volume ratio of acetone and xylene is
1:10;
[0143] (3) The mixed liquid of raw materials is added in the
reaction solvent, and the temperature rises to 50.degree. C. at the
speed of 2.degree. C./min. The mixed liquid is stirred for 40 min
at the speed of 170 rpm. Then, it is put still for 4 h under
20.degree. C. Then, aqueous phase is discarded, and organic phase
is reserved. The organic phase is washed with the sodium
bicarbonate solution with mass fraction of 1%. Then, saturated
sodium chloride is used to wash the organic phase to be neutral.
The volume ratio of organic phase, sodium bicarbonate solution and
saturated sodium chloride is 1:0.5:2 to get the pre-polymerization
solution of organic silicon resin;
[0144] (4) The glass whose weight is 0.13 times of weight of methyl
trichlorosilane is added in the organic resin prepolymer and mixed
for 20 min at the speed of 170 rmp;
[0145] (5) Xylene is removed under the conditions of 100.degree. C.
and vacuum degree 0.06 MPa to gain condensed silanol. The
temperature of condensed silanol rises to 150.degree. C., and
thermal reaction is lasted for 1.5 h to gain the glass modified
organic silicon resin.
[0146] The preparation process of Zr doped zinc oxide is as
follows: zinc nitrate water solution with the molar concentration
of 0.5 mol/L is prepared, and cetyl trimethyl ammonium bromide is
added. The solid-to-liquid ratio of cetyl trimethyl ammonium
bromide and zinc nitrate water solution is 0.009 g/mL, and they are
mixed evenly to get mixed liquid A. Sodium hydroxide water liquid
with the molar concentration of 2 mol/L is added under the stirring
condition of 230 rpm. The volume ratio of mixed liquid A and sodium
hydroxide water liquid is 1:1.2, and they are stirred for 30 min at
the speed of 230 rpm to get the material I. Zirconium dichloride
hydrate and water are mixed at the mass ratio of 1:20. Then, sodium
hydroxide whose weight is 1.9 times of weight of zirconium
dichloride hydrate is added and reacts for 40 min at the speed of
230 rpm to get the reaction liquid. The reaction liquid is
centrifuged for 25 min at the speed of 3000 rpm, and the solid at
the bottom is collected to get the material II. The material I and
the material II are mixed and heated to 150.degree. C. After
thermal insulation for 40 min, the mixture of material I and
material II is cooled to 25.degree. C., and the reaction product is
gathered. After the reaction product is washed respectively with
the water whose weight is 100 times of reaction product weight and
absolute ethyl alcohol whose weight is 70 times of reaction product
weight, it is dried for 12 h under the condition of 50.degree. C.
and vacuum degree 0.08 MPa, and smashed to particles with the grain
size of 100 nm to gain the Zr doped zinc oxide.
[0147] The method to prepare the anti-UV plastic for automobile
interior ornaments includes the following steps:
[0148] S1 PC resin and ABS resin are dried respectively for 4 h
under 85.degree. C.;
[0149] S2 PC resin, ABS resin, antioxygen 1010, pentaerythritol
stearate, pyrophyllite powder, hydroxyl modified PBO/titanium
dioxide/Zr doped zinc oxide fiber and glass modified organic
silicon resin are weighed according to the formula, and mixed for 8
min at the speed of 3000 rpm to get the mixture;
[0150] S3 The mixture is put in the extruder to extrude out. The
temperature of feeding segment of the extruder is 190.degree. C.
The temperature of mixing segment is 240.degree. C. The temperature
of machine head is 210.degree. C. The revolving speed of main
machine is 80 rpm. Then, cooling and cutting into cylindrical
particles with the diameter of 3 mm and length of 2 mm are
conducted to get the anti-UV plastic for automobile interior
ornaments.
[0151] Scratch resistance is tested for implementation example 6 by
referring to ASTM G 171-03. It is found that, no obvious scratch
can be seen with naked eyes, and the obvious scratch can be seen
when the magnifying lens is magnified for 500 times.
Test Example 1
[0152] Micro debonding method is used to test the interface
property of PBO fiber and hydroxyl modified PBO fiber. The index is
interfacial shear strength. The detailed test method refers to Liu
Xiuying's Synthesis and Characterization of Carbon Propylene Fiber
Reinforcement with Grafted Graphene Oxide in the 11th Issue of
Chinese Journal of Inorganic Chemistry 2011.
[0153] See Tab. 1 for detailed test results.
TABLE-US-00001 TABLE 1 Interface property test results Interfacial
shear strength (MPa) PBO fiber 10.85 Hydroxyl 17.14 modified PBO
fiber
[0154] It can be seen from Tab. 1 that, after hydroxyl group is
introduced, the interface adhesiveness between PBO fiber and resin
matrix is enhanced. This may be because the introduction of
hydroxyl group significantly improves surface activity of fiber,
changes conjugate electron cloud system in PBO and causes fiber
surface activation, thus enhancing interface adhesiveness property
between fiber and matrix material.
Test Example 2
[0155] Mechanical properties of anti-UV plastic for automobile
interior ornaments in implementation examples 1-6 are tested.
[0156] Tensile property is tested according to GB/T 1040-92. The
rate of tensile is 20 mm/min.
[0157] Bending property is rested according to GB/T 9341-2000. The
rate of bending is 10 mm/min.
[0158] Notch impact strength is rested according to GB/T
16420-1996. The span is 40 mm, and the depth is 2 mm.
[0159] Tensile property and bending property are conducted on the
universal material testing machine with the model of HTS-LLY9100
provided by Guangdong Zhongye Precision Equipment Co., Ltd.
[0160] Notch impact strength is carried out on the notch impact
testing machine with the model of XJJ5 provided by Chengde Jinhe
Instrument Manufacturing Co., Ltd.
[0161] The number of samples in each group of tests is 10, and the
mean value is taken as the test result.
[0162] See Tab. 2 for detailed test results.
TABLE-US-00002 TABLE 2 Mechanical property test results Tensile
Bending property property Notch impact (MPa) (MPa) strength (KJ/m2)
Implementation 48.6 53.8 67.6 example 1 Implementation 50.3 54.3
69.5 example 2 Implementation 52.9 54.6 72.8 example 3
Implementation 52.2 55.7 74.0 example 4 Implementation 53.5 56.9
77.3 example 5 Implementation 56.8 58.3 80.5 example 6
Test Example 3
[0163] The light stability of anti-UV plastic for automobile
interior ornaments in implementation examples 1-6 are tested. The
samples are fixed on the sample holder of UV accelerated aging lamp
box. The working temperature in the lamp box does not exceed
50.degree. C. Manual UVB aging experiment is conducted for the
samples. The radiation time is 400 h. The test conditions of UV
lamp box are as follows:
[0164] (1) Working size: 450.times.1170.times.500 mm
[0165] (2) Sample size: 150.times.75 mm
[0166] (3) Tube space: 35 mm
[0167] (4) Distance between sample and tube: 50 mm
[0168] (5) UV wavelength: 340 nm
[0169] (6) Power: 40 W.times.6
[0170] (7) Radiation amount: .ltoreq.50 W/cm2
[0171] See Tab. 3 for detailed test results.
TABLE-US-00003 TABLE 3 Light stability test results Tensile
strength retention rate (%) Implementation example 1 35.98
Implementation example 2 57.52 Implementation example 3 64.65
Implementation example 4 70.38 Implementation example 5 75.94
Implementation example 6 84.17
[0172] The specific implementation examples are described above. We
should understand that, common technical personnel in this field
can conceive numerous modifications and changes according to this
invention without the need of creative work. Thus, the technical
proposals gained by technical personnel through logic analysis,
reasoning or limited experiments on the basis of existing
technology should be within the protection scope confirmed in the
claim.
* * * * *